CN103874670B - Prepare the method for sulphur rankinite - Google Patents

Prepare the method for sulphur rankinite Download PDF

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Publication number
CN103874670B
CN103874670B CN201280040099.7A CN201280040099A CN103874670B CN 103874670 B CN103874670 B CN 103874670B CN 201280040099 A CN201280040099 A CN 201280040099A CN 103874670 B CN103874670 B CN 103874670B
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grog
weight
phase
scope
sintering
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CN103874670A (en
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F.布勒雅恩
D.施密特
M.本哈哈
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Heidelberg Materials AG
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Heidelberger Zement AG
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Priority claimed from EP20110006757 external-priority patent/EP2559674A1/en
Priority claimed from EP20120001488 external-priority patent/EP2636654A1/en
Priority claimed from EP20120002111 external-priority patent/EP2644577A1/en
Priority claimed from EP12002342.9A external-priority patent/EP2617691B1/en
Priority claimed from EP12003718.9A external-priority patent/EP2617692B1/en
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    • C—CHEMISTRY; METALLURGY
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    • C04B7/00—Hydraulic cements
    • C04B7/345—Hydraulic cements not provided for in one of the groups C04B7/02 - C04B7/34
    • C04B7/3453—Belite cements, e.g. self-disintegrating cements based on dicalciumsilicate
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    • C04B16/00—Use of organic materials as fillers, e.g. pigments, for mortars, concrete or artificial stone; Treatment of organic materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone
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    • C04B22/0093—Aluminates
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    • C04B22/00—Use of inorganic materials as active ingredients for mortars, concrete or artificial stone, e.g. accelerators, shrinkage compensating agents
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    • C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
    • C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
    • C04B28/06—Aluminous cements
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    • C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
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    • C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
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    • C04B7/24—Cements from oil shales, residues or waste other than slag
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    • C04B7/00—Hydraulic cements
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    • C04B7/00—Hydraulic cements
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    • C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
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    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P40/00—Technologies relating to the processing of minerals
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Abstract

The present invention relates to and there are 20 to 95% scope C by weight 5s 2$ and by weight lower than 15% C 4(A xf 1-x) 3the preparation of the sulphur rankinite grog of $, and sulphur rankinite is as the purposes of the additive for the hydraulicity and/or latent hydraulicity and/or volcanic ash shaped material.

Description

Prepare the method for sulphur rankinite
The present invention relates to and be suitable as such as the preparation of the sulphur rankinite of the additive of calcium sulphoaluminate (wustite) (belite) (CSA (F) (B))-grog ,-cement and binding agent.
The preparation of cement causes global CO 2the quite major part of output.In recent years, the ever-increasing cement demand in the whole world (especially in developing country) and for raw material, the energy and CO 2the cost of the continuous rising of certificate causes grog coefficient constantly to reduce, such as, by adding limestone powder, flying dust and Granulated slag sand as grog equivalent material.Exploitation from the byproduct of other industry and this application of waste product and alternative binding agent becomes the focus in politics, science and economy day by day.
In the whole world, generate, steel be standby, generate in precious metal extraction etc. the material hereinafter referred to as industrial by-products of enormous amount in heat energy waste treatment/energy.According to quality/composition/Application Areas, it partly or entirely can be used further in various technique and product, such as the conditioning agent in the grog preparation of portland cement (OPC), as concrete additive and as pitch and concrete aggregate etc.
Such as, but due to various factors, lack homogeneity (chemism and mineralogy) and objectionable impurities composition (organism, heavy metal etc.), the use of industrial by-products is not no problem.Especially the volume stability of the reactivity/quality of the decline of OPC-grog or the deficiency of cement can cause this type of a large amount of materials must stack with huge cost every year or be used as stockpile material and heap putting material.The stacking of this type of material also can be met difficulty, and such as leaching process may cause polluting surrounding area and waters/underground water.Therefore use/the process of industrial by-products forms significant challenge and is still open question.In the future, as far as possible effectively and sustainably utilize resource to be indispensable and in the whole world, there is meaning.
Except the grog in alternative cement and the raw material in green stock mixture, also attempt finding out other hydraulic binder.These comprise calcium sulphoaluminate-cement and contain the cement of belite as main ingredient.
Use following abbreviations common in Cement industry: H – H 2o, C – CaO, A – Al 2o 3, F – Fe 2o 3, M – MgO, S – SiO 2with $ – SO 3.Further describe to simplify, compound indicates with its pure form usually, and clearly statement mixing series/foreign ion substitute, because they are conventional in technology and Industrial materials.Any person skilled in the art understands, sign the composition of the phase mentioned in the present invention due to alternative and variable by various foreign ion, it depends on chemism and the preparation type of raw material, and wherein this compounds be the present invention cover equally and is included in the explanation of pure phase/compound.
EP1171398B1 (DE60029779T2) describes specific raw materials and sinters at 900 to 1200 DEG C, to produce the crystal X={ (C, K, N, M) with high density in stove 4(A, F, Mn, P, T, S) 3(Cl, $) } and crystal Y={ (C 2s) 3(CS) 3ca (f, cl) 2and/or crystal Z={C 5s 2$ } special grog.The cement mixing of these grogs and hydraulic cement or Portland type is produced final cement composition.
Have now found that surprisingly, phase C 5s 2$ (sulphur rankinite is also referred to as sulphur spurrite or vitriol spurrite) forms the remarkable reacting phase had in the system of al composition.Document (see such as, " SynthesisofCalciumSulfo-aluminateCementsFromAl 2o 3-RichBy-productsfromAluminiumManufac-ture ", the people such as MilenaMarroccoli., Thesecondinternationalconferenceonsustainableconstructio nmaterialsandtechnologies2010, " SynthesisofSpecialCementsfromMixturesContainingFluidized BedCombustionWaste, CalciumCarbonateandVariousSourcesofAlumina ", the people such as Belz, 28thMeetingoftheItalianSectionofTheCombustionInstitute20 05, " FluidizedBedCombustionWasteasaRawMixComponentfortheManuf actureofCalciumSulphoaluminateCements ", the people such as BelzG, 29thMeetingoftheItalianSectionofTheCombustionInstitute, 2006 and " TheFabricationofValueAddedCementProductsfromCirculatingF luidizedBedCombustionAsh ", the people such as JewellR.B, WorldofCoalAsh (WOCA) Covington, Kentucky, USA, 2007) by phase C in 5s 2that $ is described as low reactivity or inertia and be undesirable.In addition, the method avoiding this " undesirable phase " is usually pointed out.Confirm surprisingly in our experimentation, this C of significant quantity 5s 2$ phase hydration a few days ago in reacted and the phase composite of remarkably influenced hydrated sample.
Sulphur rankinite is especially suitable as the additive of hydraulic binder, wherein solidifies required aluminium and can be derived from binding agent or partially or completely be derived from added al composition.Sulphur rankinite also can excite the reaction of latent hydraulicity and/or volcanic ash shaped material.
Al composition is interpreted as the material with high-dissolvability and/or hyperergy, such as soluble alkali metal-/alkali earth metal aluminate and aluminium salt (such as Na 2al 2o 4, K 2al 2o 4, aluminum nitrate, aluminum acetate, aluminum chloride, al formate, Tai-Ace S 150 etc.), reactive and/or amorphous hydroted alumina, oxide hydroxide, synthesis or natural volcanic ash (such as metakaolin), there is high C 3a and/or high C 4the portland cement, luminite cement, calcium sulphoaluminate cement etc. of AF content or their combination.But described al composition itself not definitely must show the hydraulicity or latent hydraulicity or volcanic ash type (solidifying rigid) characteristic.
Prepare binding agent by sulphur rankinite and latent hydraulicity and/or volcanic ash shaped material and open brand-new market, application possibility and significantly can reduce CO 2generation.
Therefore, there is the demand to preparing the effective, with low cost of sulphur rankinite and the method for protection of the environment, and therefore object is be to find such method.
Described object is solved by the method preparing sulphur rankinite grog, wherein comprises at least one CaO, SiO by sintering 2and SO 3the green stock mixture in source obtains described sulphur rankinite grog, wherein so regulate sintering temperature with this sulphur rankinite-grog is contained account for grog gross weight by weight at least 20% C 5s 2$.This sulphur rankinite grog can be used as independently binding agent through grinding.Preferably this sulphur rankinite grog and other the hydraulicity and/or latent hydraulicity and/or volcanic ash shaped material are combinationally used, such as portland cement, flying dust, slag sand, annealing clay, synthetic glass etc.Correspondingly, this sulphur rankinite grog can before the milling or rear and other material be mixed to form binding agent.
Within the scope of the invention, grog is referred to and to be obtained by combustion material mixture at elevated temperatures and to contain the sintered product of at least one hydraulicity reacting phase.Cement refers to the grog ground when adding or not adding other component.Binding agent or binder mixtures refer to that it uses after interpolation water, optional adulterant and granulation stone material containing cement and hydraulic mixture that is usual but the also fine grainding component that not required that they be so is other.
Grog can be necessary with required phase containing institute and directly as binding agent after grinding to form cement.According to the present invention, obtain adhesive composition preferably by two or more grogs of mixing and/or cement, wherein before the grinding (or in process) and/or mix grinding under state and/or in binding agent preparation process.Mixing time point unless explicitly stated, following description relates in this respect the binding agent (and cement) of not circumscribed.
Unless otherwise specified, " reactivity " refers to that hydraulic is reactive.
C 5s 2the phase of $ and so on such as mainly stoichiometrically indicates, but definite composition can depart from/change.In addition, the various foreign ions from the material of halogen, nonmetal, alkali and alkaline earth metal ions and transition metal and metalloid and metal can be embedded in the crystalline structure of this phase.These are all applicable to grog of the present invention.Preference is as also having sodium and potassium to be embedded into C phosphoric acid salt, fluorochemical, boron, nitrate or muriate 5s 2in the structure of $, make its stable (such as under comparatively high temps of > 1200 DEG C) thus and/or formed more fast.Phosphoric acid salt and/or iron preferably can be embedded C 4a 3in $ phase.The embedding of foreign ion can cause this formation speed in hot-zone to improve, and this may reduce again the required residence time and/or it can be caused quantitatively to increase.Serve as those materials of fusing assistant and/or the temperature of reduction formation needed for melt, and/or promote that those materials forming grog compound (such as pass through formation mixed crystal and/or make to stablize mutually) are collectively referred to as mineralizer hereinafter.
As the title C in grog phase 4(A xf 1-x) 3the same in $, title Al 2o 3(Fe 2o 3) refer to that aluminium can part be replaced by iron, namely x is the number of 0.1 to 1.0.Usually mainly there is aluminium, with a small amount of iron of mixing, but use a large amount of iron until predominant amount also falls within the scope of the invention for iron.
Iron embeds phase C 4a 3evidence in $ is Fe-riched phase (such as Fe 3o 4, C 2f and C 4aF) quantitative minimizing, C 4a 3$ or C 4(A xfe (1-x)) 3the increase of $ phase and the increase of peak intensity and lattice parameter c () [crystallographic system: rhombic system] are from 9.1610 [No. PDF-: 01-085-2210, sulfuric acid (VI) six aluminic acid four calcium-Ca 4(Al 6o 12) (SO 4), ICSDcollectioncode:080361, uses POWD-12++ to calculate by ICSD, (1997), structure: Calos, N.J., Kennard, C.H.L., Whittaker, A.K., Davis, R.L., J.SolidStateChem., 119,1, (1995)] through 9.1784 [No. PDF-: 00-051-0162, sulfuric acid oxidation calcium ferro-aluminum-Ca 4((Al 0.95fe 0.05)) 6o 12(SO 4), ICSDcollectioncode:-, leading references: Schmidt, R., P llmann, H., Martin-Luther-Univ., Halle, Germany., ICDDGrant-in-Aid, (1999)] be increased to the highest more than 9.2000.Also can determine that occupy-place coefficient measures the formation of possible mixed crystal by Rietveld refine by the occupy-place deficiency (Unterbesetzungen) of each atom site or mixing occupy-place (Gemischbesetzungen).Another pure qualitative index is the obvious color change of grog sometimes.The color of grog such as from Chestnut/reddish brown brown through green and brown look until become light gray ashen.
Prepare sulphur rankinite targetedly or there is sulphur rankinite and be as the grog of at least one main ingredient or the advantage of cement, can in one step at usual 900 to 1200 DEG C, preferably the temperature range of 1050 to 1150 DEG C prepares sulphur rankinite or described grog.With preparation containing compared with the temperature of combustion during grog of Ye'elimit as main phase, these low combustion temperatures produce further advantage, namely can adjust the magnesium/periclasite-content (by weight > 2%) of raising in grog of the present invention targetedly.Due to described low temperature of combustion, periclasite can exist with reactive form and contribute to strength development/hydration.Also higher temperature of combustion can be used according to raw mixture, as long as form sulphur rankinite (to be preferably 20 to 100% of grog) at high proportion.
By supplying enough CaO, SiO 2and SO 3the sintering of raw material prepare C 5s 2$.On the one hand, pure or substantially pure raw material, as calcium carbonate or calcium oxide, silica powder or SILICA FUME and calcium sulfate are applicable to this object.On the other hand, natural and Industrial materials in a large number, can be used as raw material with suitable combination such as but not limited to Wingdale, bauxite, clay/claystone, calcined clay (such as metakaolin), basalt, peridotites, dunite, welded tuff, carbonatite, height and the ash material/slag/slag sand of low-quality (mineralogy/glass content, reactivity etc.), various stockpile material, red soil and brown mud, natural sulphur hydrochlorate carrier, desulfurization mud, phosphogypsum, flue gas gypsum, titanium gypsum, fluorgypsum etc. and use.Protection domain also contain meet as potential raw material minimum chemical requirements do not sign the material/material group mentioned.Raw material can but be not to carry out pre-treatment.
Sulphur rankinite also exists as mineral, does not also have the known mineral deposit that can obtain it with enough amounts or purity, although " natural " sulphur rankinite therefore can be used, but in fact uneconomical.Preferred according to the present invention by sintering that suitable raw material is prepared.
Raw material for the preparation of sulphur rankinite-grog of the present invention is ground to common fineness on per se known manner.2000 to 10000cm 2/ g, preferably 3000 to 6000cm 2/ g, particularly preferably 4000 to 5000cm 2the fineness of/g scope is suitable especially.Mesh-of-grind depends primarily on the required character of raw materials used type and composition, Fuel Process (temperature in sintering zone, the residence time etc.) and binding agent and available technological possibility.
If this preparation will obtain C pure as far as possible 5s 2$, then select except CaO, SiO 2and SO 3there is no other component outside source or only have the raw material of seldom other component.At 900 to 1200 DEG C, preferably transform calcium carbonate with silica powder and calcium sulfate in the temperature range of 1050 to 1150 DEG C and produce the C with purity > 99% 5s 2$.
But, be preparation C 5s 2$ uses the raw material of a high proportion of as far as possible low cost and environmentally compatible to be preferred." environmentally compatible " refers to and uses the least possible energy and/or protection natural matter and high-quality waste product and byproduct.
About 25% flying dust FA1(is shown in embodiment) with about 45% Wingdale K1, about 8% quartz (Merck, p.a.) and about 20%MicroA(natural anhydrite) reaction produce the C with >70% 5s 2the grog of $ content, and at ~ 8% metakaolin, ~ 58%K1, ~ 23%MicroA and ~ 10%SiO 2reaction situation in, realize the purity of >80%.
The reaction of these raw materials is preferred at 900 to 1200 DEG C equally, and preferably the temperature range of 1050 to 1150 DEG C is carried out.Be different to form C 4a 3for the purpose of $, the known sintering of same materials at least 1200 DEG C, forms sulphur rankinite substantially at this.
Possible raw material source is the parent material processed in autoclave in the preparatory stage and/or the parent material with (very) little particle-and crystallographic dimension.Very little particle-and crystallographic dimension are the sizes of 0.01-0.1 μm, and little granular size is the size of 0.1-2 μm.Parent material and/or their original mixture with (very) little particle-and crystallographic dimension can be prepared such as, but not limited to, by spraying method, sol-gel method, glycerine-nitrate process and/or polymkeric substance-precursor methods.This method has following advantage, namely described raw material just change into desired grog very fast under low temperature (such as 900-1000 DEG C), and make hydraulic hyperergy grog phase according to the heating rate regulated with due to little particle-and crystallographic dimension.
According to raw material composition, especially due to the existence of mineralizer, the higher temperature of such as to 1300 DEG C also can be suitable, such as, when there is the phosphorus (as used situation during phosphogypsum) of correlative.But be different from currently known methods/grog, the present invention is devoted to form sulphur rankinite, is therefore formed for it and optimize sintering temperature.At these tem-peratures, outside sulphur removal rankinite, the reactive polymorphic form of more Dicalcium Phosphate (Feed Grade) can be produced.In contrast, in the prior art, for C 4a 3sintering temperature is optimized in the formation of $, and should not form sulphur rankinite as far as possible.
On the contrary, according to the present invention, selective temperature like this to form sulphur rankinite as much as possible, if raw material contains Al 2o 3or Fe 2o 3source, then by C 4(A xf (1-x)) 3the content of $ is limited in and is less than 20%, is preferably less than 15%.Although also can use containing more C 4(A xf (1-x)) 3the grog of $, but its more high-content is unfavorable for sulphur rankinite, and corresponding higher sintering temperature also adversely can affect the reactivity of sulphur rankinite.
900 DEG C to 1300 DEG C, preferably the temperature range of 1050 DEG C to 1150 DEG C should keep 10 minutes to 180 minutes, preferably 25 minutes to 120 minutes, more more preferably time of 30 minutes to 60 minutes.In order to the phase in process of cooling further needed for formation, grog can stand 5 minutes to 120 minutes the scope of 900 DEG C to 750 DEG C, the preferably time of 10 minutes to 60 minutes.Finally, or also do not cooled by the range delay at 900 DEG C to 750 DEG C, and grog is cooled in a known way fast, to prevent extra phase transformation.
The reactivity of described grog is such as by improving fineness and/or C 2the content of S targetedly, according to the various requirement of binding agent, carries out regulating or optimizing.This is equally by adding in raw material by mineralizer, and wherein a part of Dicalcium Phosphate (Feed Grade) to major portion is as C 2the α polymorphic form of S and/or with mixed crystal or doping " α " C 2the form of S, such as, at P 2o 5as calcium-phosphate-silicate [Ca under existence 2siO 40.05Ca 3(PO 4) 2] exist.This contributes to or causes forming at least one melt (such as at CaO – SiO 2– CaSO 4in – ± mineralizer system or at CaO – Al 2o 3(Fe 2o 3) – SiO 2– CaSO 4calucium Silicate powder melt in – ± mineralizer system).
In addition, found heating rate surprisingly and used mineralizer (such as Ca 3p 2o 8, CaF 2, K 2pO 4, Na 2pO 4, Na 2cO 3, K 2cO 3, FeCl 3, MgCl 2, Na 2[B 4o 5(OH) 4] 8H 2o, BaSO 4, etc.) there is remarkably influenced to the composition of grog and the amount of reacting phase and content.High heating rate, such as, be greater than 1000 DEG C/min, is preferably greater than 2000 DEG C/min, is especially greater than 3500 DEG C/min, stabilizes C even at higher temperatures 5s 2$, as employed mineralizer.By stove is adjusted to desired target temperature, by described raw material at the corresponding temperature direct sintering realize high heating rate.Under lower heating rate, except except sulphur rankinite, form α C more 2the polymorphic form of S and α C 2the mixed crystal of S and mineralizer.
The formation of melt controls pointedly by selecting being added with of heating rate, maximum combustion temperature, rate of cooling and/or mineralizer.
According to the present invention, comprise C 5s 2$ is as the grog of main ingredient or contain following component by not having additive to grind the cement obtained with shown content by it:
C 5s 2$ by weight 20 to 100%, preferably 30 to 95%, more more preferably 40 to 90%
(α, β) C 2s by weight 0 to 80%, preferably 5 to 70%, more more preferably 10 to 60%
C 4(A xf (1-x)) 3$ is 0 to <15% by weight, and preferably 3 to 12%, more more preferably 5 to 10%
C 2(A yf (1-y)) by weight 0 to 30%, preferably 5 to 20%, more more preferably 8 to 15%
Reactive aluminum hydrochlorate by weight 0 to 20%, preferably 1 to 15%, more more preferably 3 to 10%
Periclasite (M) by weight 0 to 25%, preferably 1 to 15%, more more preferably 2 to 10%
Secondary phase by weight 0 to 30%, preferably 3 to 20%, more more preferably 5 to 10%,
Based on the total amount of grog/cement, wherein the content of these phases adds up to 100%.
Title (α, β) C 2s means that this can be C 2polymorphic form of S and composition thereof, wherein reactive α polymorphic form (such as α, α ' l, α ' h) be preferred.Preferably comprise at least 5%C by weight 2the α polymorphic form of S, because these advantageously contribute to high early strength.
By mineralizer is added in raw material, a part to major portion Dicalcium Phosphate (Feed Grade) can using as doping " α " C 2the mixed crystal form of S, such as, at P 2o 5as calcium-phosphate-silicate [Ca under existence 2siO 40.05Ca 3(PO 4) 2] exist.Such compound drops on reactive α C equally 2in S polymorphic form and scope of the present invention.Depend on the amount of interpolation, heating rate etc., the mineralizer that may exist can be embedded into such as C equally 5s 2in the structure of $.
At C 4(A xf (1-x)) 3in $ phase, x 0.1 to 1, the preferably scope of 0.8 to 0.95.At C 2(A yf (1-y)) mutually in, y 0.2 to 0.8 scope, the preferably scope of 0.4 to 0.6.
Reactive aluminum hydrochlorate should be understood to such as, but not limited to, C 3a, CA and C 12a 7.
Secondary can be such as mutually, but be not limited to, the form of the material of basic metal/alkaline earth metal sulphate, quartz, spinel, peridotites, pyroxene, melilith system and merwinite system, phosphatic rock, ellestadite, calcium silicophosphate, free lime, spurrite, quartz and/or X-ray amorphous phase state/glassy phase, ratio is by weight 0 to 30%, preferably 2 to 20%, particularly preferably 5 to 15%.Free lime content in grog by weight lower than 5%, preferably lower than 2%, particularly preferably lower than 1%.In a preferred embodiment, this sulphur rankinite grog contains by weight 1 to 10%, and preferably 2 to 8%, the more preferably at least one x-ray amorphous phase/glassy phase of 3 to 5%.
Especially the sulphur rankinite grog comprising x-ray amorphous phase state/glassy phase is not disclosed so far, and also fails to find in patent EP1171398B1.
Containing C 5s 2$ is as main phase and the content of the main oxides of the grog made separately comprises following scope:
CaO by weight 40 to 70%, preferably 45 to 60%, more more preferably 50 to 55%
SiO 2by weight 5 to 30%, preferably 10 to 25%, more more preferably 15 to 23%
SO 3by weight 3 to 30%, preferably 5 to 26%, more more preferably 8 to 22%
∑ (Al 2o 3+ Fe 2o 3) by weight 0 to 40%, preferably 5 to 30%, more more preferably 8 to 20%
MgO by weight 0 to 25%, preferably 2 to 15%, more more preferably 5 to 10%,
Based on the total amount of grog/cement, wherein the ratio of these content adds up to 100%.
Also be not yet disclosed so far and prepare C targetedly 5s 2$ grog, C 5s 2the α C of $ stabilization at relatively high temperatures, possible raising 2the formation of at least one melt and the sulphur rankinite grog application in the early strength improving binding agent as additive and the rich aluminium system of reactivity in the synthesis speed of S, the mixed crystal of Dicalcium Phosphate (Feed Grade) and grog.This is the brand-new raising hydraulicity and the early strength of latent hydraulicity binder system and/or the method for weather resistance.
For preparing cement or binder mixtures, the sulphur rankinite maybe can prepared prepared in accordance with the present invention or the grog being rich in sulphur rankinite together with one or more or all other binder components to be ground or individually, with or be not ground to 2000 to 10000cm in a way known together with extra vitriol carrier 2/ g, preferably 3000 to 6000cm 2/ g, particularly preferably 4000 to 5000cm 2the common cement fineness (according to Blaine) of/g.
As vitriol carrier it is particularly suitable that basic metal-and/or alkaline earth metal sulphate, preferably with the form of gypsum and/or semihydrate and/or anhydrite and magnesium sulfate, sodium sulfate and potassium sulfate.Because in this reaction process, sulphur rankinite provides vitriol equally, so also or other vitriol carrier can not had to obtain the binding agent being easy to process with a small amount of other vitriol carrier.
Containing main phase C 5s 2the grog of $ (content such as but not limited to by improving reactive aluminum hydrochlorate and ferrate) can be used as independently binding agent under suitable composition.But, more favourable by its such as with Portland-, calcium sulphoaluminate (wustite) (belite)-, calcium aluminate-grog ,-cement or-binding agent be merged into the binding agent having and optimize and form.
Can by hydraulic reactive explosive as calcium aluminate, aluminous cement, calcium sulphoaluminate, calcium sulphoaluminate cement, geopolymeric cement and/or latent hydraulicity material as burned resinous shale, gehlenite glass or their combination add to as described in binding agent.The mixture with the hydraulicity or potential hydraulic reactive component is optional for the available hydraulic reactivity of acquisition, and on the contrary, the sulphur rankinite grinding to form cement demonstrates desired hydraulic reactivity by combining with non-hydraulic reactive aluminum source.
This binding agent is preferably also containing adulterant and/or additive and other hydraulically active component optional.This additive can be latent hydraulicity, volcanic ash type and/or non-hydraulic activity (Wingdale/rhombspar, the precipitate C aCO that such as grind 3, Mg (OH) 2, Ca (OH) 2, aluminium hydroxide [such as amorphous Al (OH) 3], solvable alkali metal aluminate [such as Na 2al 2o 4], silica flour) component.
This cement or binder mixtures preferably also containing one or more solidify-and/or hardening accelerator as adulterant, its be preferably selected from there is available aluminium or when contact with water discharge such as with Al (OH) - 4or amorphous Al (OH) 3the component of the aluminium of gel form, such as, but not limited to, solvable alkali metal aluminate [such as Na 2al 2o 4, K 2al 2o 4deng], aluminium hydroxide (such as amorphous Al (OH) 3).In addition, this cement or binder mixtures can combine containing the same said components with having available aluminium one or more solidify-and/or hardening accelerator as adulterant, be preferably selected from lithium salts and lithium hydroxide, other an alkali metal salt and alkali metal hydroxide and alkalimetal silicate.
Improve the pH value of this solution in addition and therefore improve C 5s 2reactive additive of $, such as alkali metal aluminate and an alkali metal salt, alkalimetal silicate and alkali metal hydroxide particularly preferably and can with by weight 0.1 to 10%, preferably 0.5 to 5%, more more preferably 1 to 2% amount be metered into.
More preferably containing following material: concrete liquefying agent and/or water reducer and/or retardant, be preferably based on sulfonated lignin, sulfonation naphthalene-, trimeric cyanamide-or phenol formaldehyde condensate, or based on acrylic acid-acrylamide mixture or polycarboxylate ether, or based on phosphorylation polycondensate, phosphorylation alkyl carboxylic acid and salt thereof, (hydroxyl) carboxylic acid and carboxylate salt, borax, boric acid and borate, oxalate, sulfanilic acid, aminocarboxylic acid, Whitfield's ointment and acetylsalicylic acid, dialdehyde.
Can with the grinding of pole lower power intake containing C 5s 2the grog of $, if especially this grog contains seldom other phase, so that can by grinding or pre-grinding are adjusted to containing C separately 5s 2the larger fineness of the grog of $, if such as need C 5s 2the more hyperergy (faster response/consumption) of $.Require if this is special purpose, the product through grinding can have d 50be less than 20 microns and d 90be less than 100 microns, or d 50be less than 5 microns and d 90be less than 20 microns, or d 50be less than 0.1 micron and d 90be less than the size-grade distribution of 2 microns.
Containing C 5s 2the strong grinding of the grog of $ may cause phase state (the such as C of this grog 5s 2$) partly (usual 3 to 20%) to almost completely (>90%) be that x-ray is unbodied.This significantly improves along with reactive and allow to prepare novel hyperergy binder system.
In cement of the present invention or the course of processing containing its binding agent, the water/binding agent value of 0.2 to 2 is suitable, is preferably 0.3 to 0.8, particularly preferably 0.45 to 0.72.
According to quality and the composition of available raw material or grog, independently component or component mixture can be used to prepare binding agent.
The cement obtained with sulphur rankinite (grog) prepared in accordance with the present invention or another advantage of binder mixtures be made up of it are in hydro-combination process, form not homophase (such as ettringite [AF t], single-phase [AF m], metal-metal hydroxy salt [LDH] etc.), each heavy metal species and other objectionable impurities (such as muriate etc.) can to embed in its structure and to be therefore permanently fixed them by they.
Explain the present invention based on the following example, but and be not intended to be limited to described specific embodiments.Unless forced unless otherwise specified or in literary composition to make contrary regulation, per-cent is based on weight; As having a question, based on the gross weight of this mixture.
The invention still further relates to all possible combination of preferred embodiment, as long as they do not repel mutually.The term " roughly " relevant to numeric data or " approximately " comprise the value of at least high or low 10%, or the value of high or low 5%, comprise the value of high or low 1% in any situation.
Embodiment
In table 2, based on their oxidized form main component and the raw material of mesh-of-grind sign for carrying out following embodiment thereof.Be given in the weight loss after annealing at 1050 DEG C equally.Table 3 shows the mineralogy phase composite of industrial by-products used.
Table 2: raw materials used essentially consist (RFA)
Raw material Wingdale Flying dust Vitriol carrier Al Korr. Metakaolin
Sample K1 FA1 MicroA Al(OH) 3 MK
RFA Unit
GV 1050°C % 43.09 0.82 4.64 34.64 1.91
SiO 2 % 1.53 28.50 4.17 0.00 48.00
Al 2O 3 % 0.35 12.50 1.36 65.36 41.60
TiO 2 % 0.03 1.05 0.04 0.00
MnO % 0.01 0.18 0.00 0.00
Fe 2O 3 % 0.19 5.18 0.37 0.00 1.80
CaO % 54.50 37.40 37.40 0.00 5.70 7 -->
MgO % 0.22 4.81 1.82 0.00 0.10
K 2O % 0.04 0.28 0.28 0.00 0.95
Na 2O % 0.00 0.07 0.06 0.00
SO 3 % 0.01 7.71 49.80 0.00
P 2O 5 % 0.01 1.27 0.00 0.00
Amount to 99.98 99.77 99.94 100.00 100.06
Amorphous % / 38.0 / / >95
Density g/cm3 2.64 2.82 2.54
According to the mesh-of-grind of Blaine cm 2/g 3350 4380
Table 3: mineral facies composition (QXRD according to Rietveld) of flying dust FA1 used
Mineral Unit
Quartz % by weight 11.5
Cristobalite % by weight 0.4
Free lime % by weight 9.3
Periclasite % by weight 2.8
Anhydrite % by weight 10.4
Gehlenite % by weight 6.3
Merwinite % by weight 4.9
Maghemite % by weight 1.2
Rhombohedral iron ore % by weight 0.9
Ye'elimite % by weight 3.1
C 2S % by weight 8.1
C 4AF % by weight 3.1
Amorphous % by weight 38.0
embodiment 1T pur
CaCO 3[Merck, p.a.], CaSO 4the stoichiometric mixture of [Merck, p.a.] and silica powder [Merck, p.a.] burns 1 hour at 1100 DEG C, then cools fast, and grinding is also again burnt 1 hour and cooling fast at 1100 DEG C.
embodiment 2TK fA
Raw mixture is by 45% Wingdale (K1)+27%FA by weight 2, 20%MicroA and 8% silica powder (Merck, p.a.) forms.These raw material sinter and impose the cooling program for annealing after sintering at 1100 DEG C, and wherein temperature was down to 850 DEG C through about 35 minutes from 1100 DEG C.Subsequently this grog is cooled in atmosphere fast.
embodiment 3TK aGS
Raw mixture is by 58%K1+8%MK, 24%MicroA and 10% quartz powder (Merck, p.a.) are formed by weight.Program in the same manner as in Example 2 is imposed to these raw material.
embodiment 4
Different binding agents is mixed into by business CSA cement (forming in table 6) with from three kinds of quality sulphur rankinites of embodiment 1 to 3 and MicroA.The composition row of sulphur rankinite in table 4, arrange in table 5 with the ratio of mixture of cement; Fig. 1 a, Fig. 1 b, Fig. 2 a, Fig. 2 b, when Fig. 3 a, Fig. 3 b, Fig. 4 a and Fig. 4 b are given in and stir with the W/B value of 0.7 and water, the hot-fluid of these mixtures and accumulation hot-fluid.The TG data (chemically-bonded water) of cement building stones (being normalized to 100% slurry) that table 7 provides the mineralogy (QXRD according to Rietveld) of the cement corresponding to embodiment 4 and cement and is made up of it; W/Z value 0.7.
Table 4: from chemistry (calculating) and the mineralogy composition of the grog of embodiment 1 to 3
Oxide compound T pur TK FA TK AGS
SiO 2 25.00% 21.30% 22.16%
Al 2O 3 -- 4.75% 4.94%
TiO 2 -- 0.38% 0.04%
MnO -- 0.07% 0.01%
Fe 2O 3 -- 1.96% 0.45%
CaO 58.34% 53.20% 55.34%
MgO -- 2.23% 0.77%
K 2O -- 0.19% 0.22%
Na 2O -- 0.04% 0.02%
SO 3 16.66% 15.44% 16.06%
P 2O 5 -- 0.44% 0.01%
Phase
Anhydrite 0.4 0.3 0.2
C 3A (cubic crystal) -- 2.2 --
C 3A (iris) -- 1.2 0.4
C 2S a`H -- 2.7 1.4
C 2S β -- 5.7 3.2
C 2S γ -- 1.1 0.4
∑C 2S -- 9.5 5.0
Sulphur rankinite 99.2 74.9 85.5
Free lime <0.1 0.3 0.3
Periclasite -- 1.2 0.5
C 4A 3S -- 9.3 7.0
Pyroxene -- 1.2 1.1
Quartz 0.4 -- --
Ratio
CaO/Al 2O 3 -- 11.21 11.21
Al 2O 3/Fe 2O 3 -- 2.42 10.92
SO 3 / (Al 2O 3+Fe 2O 3) -- 2.30 2.98
SO 3/SiO 2 0.67 0.72 0.72
CaO/SO 3 3.50 3.45 3.45
CaO/SiO 2 2.33 2.50 2.50 9 -->
MgO/SiO 2 0.00 0.10 0.03
Table 5: business calcium sulphoaluminate-cement and the mixture corresponding to the grog of embodiment 1-3
Mixture CSA T pur TK FA TK AGS MicroA
CSA-C$ 85% 15%
CSA-T 60% 40%
CSA-T-C$ 68% 20% 12%
CSA-TK_FA-C$ 68% 20% 12%
CSA-TK_AGS-C$ 68% 20% 12%
Table 6: the chemical constitution of business calcium sulphoaluminate-cement used
China CSA
GV 1050°C % 0.18
SiO 2 % 6.93
Al 2O 3 % 36.48
TiO 2 % 1.64
MnO % 0.00
Fe 2O 3 % 2.24
CaO % 40.61
MgO % 2.94
K 2O % 0.18
Na 2O % 0.00
SO 3 % 8.61
P 2O 5 % 0.14
Amount to % 99.94
Table 7: the cement of embodiment 4 and the mineralogy of cement building stones
Example5
0.1 % by mole of Ca will be with or without 3p 2o 8with constant CaO-SiO 2ratio by CaCO 3[Merck, p.a.], CaSO 4[Merck, p.a.], silica powder [Merck, p.a.] stoichiometric mixture formed at different temperature and burn 1h by different heating rate (be heated to target temperature contrast from 20 DEG C in 30 minutes and directly introduce raw material under target temperature), then cool fast, grind and 1h also cooling fast of again burning under target temperature.This gives sulphur rankinite grog different qualities.Respectively C is shown in Fig. 5 and 6 5s 2$ (■), α C 2s (◇), β C 2the amount of S (▲) and free lime (●) is to the dependency of top temperature during sintering.The value of black obtains under the normal heating speed of about 40 DEG C/min, and the value of grey obtains under the high heating rate of about 4000 DEG C/min.
Confirm, add the mineralizer formation (free lime content lower) that can accelerate/be conducive to grog phase the same as high heating rate, cause forming reactions α C 2s polymorphic form, stablizes C at higher temperature (>1200 DEG C, see Fig. 5 and 6) 5s 2$ and formation x-ray amorphous phase.
embodiment 6
Sulphur rankinite grog according to embodiment 1 is ground to form two kinds of fineness.Fig. 7 illustrate with 0.5 W/B and water stir time the hot-fluid of sulphur rankinite through grinding and accumulation hot-fluid.
Confirm, the raising of fineness significantly improves phase C 5s 2the reactivity (see Fig. 7) of $.

Claims (20)

1. prepare the method for sulphur rankinite grog, it is characterized in that, sintering is at least containing CaO, SiO 2and SO 3the green stock mixture in source, wherein in sintering process 900 to 1300 DEG C of range regulation temperature, with the C making described sulphur rankinite-grog have 20 to 95% scopes by weight 5s 2the C of $ content, by weight 5 to 80% scopes 2s content and be the C of 0.1-1 lower than the x of 15% by weight 4(A xf 1-x) 3$ content, respectively based on the total weight of described grog.
2. method according to claim 1, is characterized in that described green stock mixture comprises Al in addition 2o 3source and Fe 2o 3source.
3. method according to claim 1, is characterized in that, makes C by being embedded in crystalline structure by one or more foreign ions of the material being selected from nonmetal and metal 5s 2$ stabilization.
4. method according to claim 3, is characterized in that, adding in described raw material provides phosphoric acid salt, fluorochemical, alkali, nitrate and/or muriatic material.
5. method according to claim 3, is characterized in that, temperature during sintering is the scope of 1100-1300 DEG C.
6. method according to claim 1, is characterized in that, regulates the heating rate of 10-6000 DEG C/min of scope.
7. method according to claim 1, is characterized in that, temperature during described sintering is the scope of 900-1200 DEG C.
8. according to the method for one of claim 1-7, it is characterized in that, except C 5s 2$ and C 4(A xf (1-x)) 3$ and outer, described grog comprises 0-30%C by weight 2(A yf (1-y)), wherein y is in the scope of 0.2-0.8, by weight 0-20% reactive aluminum hydrochlorate, and 0-25% periclasite and the by weight secondary phase of 0-30% by weight, based on the total amount of grog, the content of wherein said phase adds up to 100%.
9. method according to claim 8, is characterized in that, the scope of at least one X-ray amorphous phase/glassy phase 1-10% by weight exists mutually as secondary.
10. according to the method for one of claim 1-7, it is characterized in that, being ground to according to Blaine by described sulphur rankinite grog is 2000cm 2/ g-6000cm 2the fineness of/g.
11. according to the method for one of claim 1-7, and it is characterized in that, being ground to according to Blaine by described sulphur rankinite grog is 5000-10000cm 2the fineness of/g.
12., according to the method for one of claim 1-7, is characterized in that, are ground to according to Blaine described sulphur rankinite grog more than 10000cm 2the fineness of/g, and the phase state of the described grog of 3-99% exists with X-ray amorphous form.
13. methods according to claim 4, is characterized in that, temperature during described sintering is the scope of 1100-1300 DEG C.
14. according to the method for one of claim 1 or 2 or 6, it is characterized in that, temperature during described sintering is the scope of 1050-1150 DEG C.
15. methods according to claim 8, is characterized in that, at least one X-ray amorphous phase/glassy phase exists as secondary mutually by the scope of 2-8% by weight.
16. methods according to claim 10, is characterized in that, described fineness is 3000cm according to Blaine 2/ g-5000cm 2/ g.
17. methods according to claim 11, is characterized in that, described fineness is 7000cm according to Blaine 2/ g-9000cm 2/ g.
18. methods according to claim 12, is characterized in that, the phase state of the described grog of 5-50% exists with X-ray amorphous form.
19. methods according to claim 15, is characterized in that, the scope of at least one X-ray amorphous phase/glassy phase 3-5% by weight exists mutually as secondary.
20. methods according to claim 3, is characterized in that, by being selected from halogen, alkali and alkaline earth metal ions, and one or more foreign ions of transition metal and metalloid material are embedded in crystalline structure and make C 5s 2$ stabilization.
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